Manufacture of thiazole derivatives



Patented Mar. 12, 1940 I MANUFACTURE OF THIAZOLE DERIVATIVES Marion W. Harman, Nitro, W. Va., assignor to Monsanto Chemical Company, St. Louis, Mo., a corporation of Delaware No Drawing. Original application January 22,

1932, Serial No. 588,227. Divided and this application Januaryl3, 1938, Serial No. 184,903

19 Claims. (01. 260306) The present invention relates to a process for possess the following modulus and tensile vulcanization of rubber and similar products characteristics: and to the products obtained thereby, and is Table I particularly directed to the acceleration of the vulcanization step-by employing in that step the M 6 odulusofelasticityin reaction product oi a meicapto aryl thiazole, for Cure 1m linjatelongmons example an alkali metallic salt of mercaptoof- Tensile benzo-thiazole, and a halogenated alkyl carbonyl at containing compound. Time Pounds v Percent It ispreferred that the present class of acmin- 32; 300% 500% 700% 10 celerating materials be employed in conjunction qwith a basic organic nitrogen containing acl r l 20 10 00 130 300 1660 1050 celerating compound, pieferably a guanidine, for v 30 10 126 208 648 2360 950 example diphenyl guamdme, to form a mixed 30 g8 17? 403 3 5 5 860 .v v 45 21 525 5 s30 l5 a'ccelelatm' 6O 20 241 03s a 2700 4200 790 One of the preferred class of compounds, for so 264 756 3055 4705 780 example the reaction product of mono chlor acetone and the Sodmm salt of mercaptmbenzo' The data set forth in Table I show that the q has been. Prepared according t0 the preferred class of accelerators when activated 20 follo'wmg manner: by a basic organic nitrogen containing accelerat-"go Substantlally 9 mol (18-9 Parts) of the ing compound possesses very desirable acceleratsodium salt of mercapto-benzo-thiazole was dismg properties; solved in a suitable solvent, for example 80 parts Another of t preferred class of rubber I by Weight of ethylralcohol, and Substantially vulcanization accelerators comprises the reaction a of a mol (9.3 parts) of mono chloracetone added prgduct of chloracetophenone d a mercapto;

w y e t t room t mp at After the benzo-thiazole, for example the sodium salt of reaction was complete, the sodium chloride mercapto-benzothiazole. One method whereby was filtered Off and the filtrate, added this material has been prepared follows:

to a weak alkaline solution, for example sodium Substantially H101 (139 parts) of the sodium.

a nat solution, w up after filtering d salt of mercapto-benzo-thiazole was dissolved in" 30 Washing the. material thereby precipitated with a suitable quantity of water and substantially 0.1 water, a good yield of the preferred accelerator mol (15.4 parts) of chloracetophenone dissolved was obtained in the form of a solid havin a n a sm a unt f a r ani so v nt, for

-me1ting range f 4 to 7 C example acetone, added slowly thereto with The product prepared as described was cooling. Thel1ght yellow precipitate comprising co-rporated in a typical gum stock and found to h reactlon Product w filtered Off F f Washed possess accelerating properties. Preferably, how- Wlth an alkalme solutlon so i eliminate any ever, the material is employed in conjunction with unfiacted mezjcapto'benzo-thlazole'. The

A0 a basic organic nitrogen containing accelerating 2 prepared the manner descnbed was 40 alned in good yield and melted at 106 to 109 C. compound Thus a rubber stock was compound The reaction product of the sodium salt of ed m the Well known manner complilsmg mercapto-benzo-thiazole and chloracetophenone parts of pale crepe rubber 5 Parts of Zmc Oxlde, when employed alone in a typical rubber stock 3 Parts of sulfur, Part of diphenyl guanidine was found to possess accelerating properties. It. 45

P of the reactior} Product of Substantially is preferable, however, that said reaction product v equi-molecular proportions of mono chlor acetone be oy in conjunction with a basic organic and the sodium Sa t of merca'pto-benzo-thiazolenitrogen containing rubber vulcanization acceler- The rubber stoc after curing in a press in the ator Thus a rubber stock was compounded in well known manner, on testing was found to the wellknown manner comprising parts of; 50

pale crepe rubber, 5 parts of zinc oxide, 3 parts of sulfur, 0.6 part of diphenyl guanidine, 0.4 part of the reaction product of substantially equi-"nolecular proportions of chloracetophenone and the sodium salt of mercapto-benzo-thiazole. The rubber stock thus compounded was vulcanized by heating in a press in the well known manner, and the cured rubber stock after testing was found to possess the following tensile and modulus characteristics:

The data set forth in Table II show clearly that the preferred class of compounds forms an important group of rubber accelerators when employed in conjunction with a basic organic nitrogen containing vulcanization accelerator to form a mixed accelerator.

The reaction product of substantially equi-molecular proportions of chloracetophenone and the sodium salt of mercapto-benzo-thiazole has also been employed in a tread stock.

As other examples of the preferred class of accelerating compounds, the following materials have been prepared in a manner similar to that hereinbefore set forth.

(a) Reaction product of substantially equimolecular proportions of the sodium salt of mercapto-benzo-thiazole and chloracetanilid having a melting range of l13121 C.

(1)) Reaction product of substantially equi-molecular proportions of chloracetamid and the sodium salt of mercapto-benZo-thiazole having a melting range of 142-bit C.

(c) Reaction product of substantially equimolecular proportions of the sodium salt of mercapto-benzo-thiazole and chloracet-o-chloranilide having a melting range of ll5-ll8 C.

((1) Reaction product of substantially equimolecular proportions of chloracet-p-nitranilide and the sodium salt of mercapto-benzo-thiazole having a melting range of 150-152 C.

(e) Reaction product of substantially equi-molecular proportions of chloracet-o-toluidide and the sodium salt of mercapto-benzo-thiazole having a melting range of 145-149 C.

All of the above materials have been employed alone, but preferably are employed in conjunction with a basic organic nitrogen accelerator, in a typical rubber stock. As examples of their use in conjunction with a basic organic nitrogen containing accelerator, each of the above accelerators, (a), (b), (c), (d) and (8), were incorporated separately in a rubber stock comprising:

Parts Pale crepe rubber Zinc oxide 5 Sulfur 3 One of the preferred accelerators (a) to (e) inclusive 0.4 Diphenyl guanidine 0.6

On testing strips of the above described stocks, vulcanized by heating in a press for different periods of time under temperatures given by different steam pressures, the tensile and modulus data obtained show that the preferred accelerators (a) to (e) inclusive, described above exhibit the accelerating properties of the class.

Other basic organic nitrogen containing vulcanization accelerators than diphenyl guanidine have been employed in conjunction with the preferred class of materials. Thus, diacetone amine and piperidine have been employed in a typical rubber stock in conjunction with the preferred class of accelerators, for example, the reaction product of substantially equi-molecular proportions of chloracetamid and the sodium salt of mercapto-benzo-thiazole, and found to be activators thereof.

Other mercapto-aryl-thiazoles than mercaptobenzo-thiazole may be reacted with a halogenated alkyl carbonyl containing compound. Thus, mercapto-tolyl thiazole, mercapto xylyl thiazole, mercapto-naphthiazole and the like may be reacted with mono-chloracetone, dichloracetone, chlor methyl ethyl ketone, chloracetophenone, chloracetamide, chloracetanilid, chloracet-o-chloranilide, chloracet-p -nitranilide, chloracet-o-toluidide, chlor diethyl ketone and analogous compounds and the reaction products employed as rubber accelerators. Again, mercapto-benzo-thiazole, or a salt thereof, preferably an alkali metallic salt, may be reacted with chlormethyl ethyl ketone, dichlor acetone and chlor diethyl ketone and the reaction products employed as rubber vulcanization accelerators. Furthermore, other basic organic nitrogen containing accelerators than those hereinbefore set forth may be employed in conjunction with the preferred class of compounds as activators thereof. Thus, 2,4 diamino diphenyl amine, diortho-tolyl-guanidine and the like may be so employed.

The foregoing examples are to be illustrative only and not at all limitative of the invention. Other vulcanized products may be obtained by employing other compounding ingredients and other proportions of ingredients than those particularly set forth in the examples given.

This is a division of co-pending application, Serial No. 588,227, filed January 22, 1932, Patent 2,109,698.

What is claimed is:

l. A method of. making a chemical compound comprising reacting a mercapto-aryl-thiazole containing no group more reactive toward an alkyl halogen atom than the mercapto group and a ketone composed of the elements carbon,

hydrogen, oxygen and halogen containing a halogenated alkyl group.

2. A method of making a chemical compound comprising reacting a salt of a mercaptoarylthiazole containing no group more reactive toward an alkyl halogen atom than the mercapto group and a ketone composed of the elements carbon, hydrogen, oxygen and halogen containing a halogenated alkyl group.

3. A method of making a chemical compound comprising reacting an alkali metal salt of a mercapto-benzo-thiazole containing no group more reactive toward an alkyl halogen atom than the mercapto group and a ketone composed of the elements, carbon, hydrogen, oxygen and halogen containing a halogenated alkyl group.

4. A method of making a chemical compound comprising reacting in an organic solvent an alkali metal salt of amercapto-benzo-thiazole containing no group more reactive toward an alkyl halogen atom than the mercapto group and a ketone composed of the elements carbon, hydrogen, oxygen and halogen Containing a halogenated alkyl group.

5. A method of making a chemical compound which comprises combining a water solution of an alkali metal salt of a mercapto-benzo-thiazole containing no group more reactive toward an alkyl halogen atom than the mercapto group and an organic solvent solution of a ketone composed of the elements carbon, hydrogen, oxygen and halogen containing a halogenated alkyl group and efiecting the reaction.

6. A method of making a chemical compound which comprises combining a water solution of an alkali metal salt of a mercapto-benzo-thiazole containing no group more reactive toward an' alkyl halogenatom than the mercapto group and a solution in an organic solvent of a halogenated aliphatic ketone composed of the elements car-- bon, hydrogen, oxygen and halogen and effecting the reaction.

7. A method of making a chemical compound comprising reacting in an organic solvent an alkali metal salt (of a mercapto-benzo-thiazole containing no group more reactive toward an alkyl halogen atom than the mercaptogroup and a halogenated aliphatic keton'e composed of the elements carbon, hydrogen, oxygen and halogen. i

8. A method of making a chemical compound comprising reacting an alkali metal salt of a 1nercapto-benzo-thiazole containing no group more reactive toward an alkyl halogen atom than the mercapto group and chloracetone.

9. A method of making a chemical compound comprising reacting in ethyl alcohol an alkali metal salt of. a mercapto-benzo-thiazole containing no group more reactive toward an alkyl halogen atom than the mercapto group and mono chloracetone.

10. A method of making a chemical compound comprising reacting in ethyl alcohol the sodium salt of mercapto-benzo-thiazole and mono chloracetone.

11. A method of making a chemical compound:-

which comprises combining a water solution of an alkali metal salt of a mercapto-benzo-thiazole containing no group more reactive toward an alkyl halogen atom than the mercapto group and a solution of chloracetophenone in an organic solvent miscible with water and effecting the reaction.

12. A method of making a chemical compound which comprises combining a water solution of the sodium salt of mercapto-benzo-thiazole and an acetone solution of chloracetophenone and efiecting the reaction.

13. A chemical compound of the formula ence of an organic solvent in which alkali metal halides are relatively insoluble, but in which the condensation product of said mercapto-arylthiazole and said halogensubstituted ketone is soluble, separating the precipitated alkali metal halide, treating the filtrate with a dilute aqueous alkaline solution, separating and drying the precipitated product.

. 15. A method of making a chemical compound comprising reacting an alkali metal salt of a mercapto-aryl-thiazole containing no group more reactive toward an alkyl halogen atom than the mercapto groupand a halogenated aliphatic ketone composed of the elements carbon, hydrogen, oxygen and halogen in the presence of ethyl alcohol, filtering ofi the alkali metal halide,

treating the filtrate with a dilute aqueous alka-- line solution, separating and drying the precipitated solid.

16. A method of making a chemical compound comprising reacting the sodium salt of mercaptobenzo-thiazole and chlor acetone in the presence of ethyl alcohol, filtering off the sodium chloride;

in I

treating the filtrate with a dilute aqueous alkaline solution, separating and drying the precipitated product.

17. A chemical compound of the formula [RrS-]nR-CO where n is an integer less than three, R is an aryl thiazole, R is an alkyl radical and R" is a hydrocarbon group.

l8. A chemical compound of the formula [R-S-lnR'-COR" where n is an integer less than three, R is a benzotl'n'azole, and R and R! are alkyl groups.

19. A chemical compound of the formula R--S-CH2-CO-CI-I2 where R is a benzothiazole.

MARION W. HARMAN. 

